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Comparative spectroscopic and mechanistic study of chelation properties of fisetin with iron in aqueous buffered solutions. Implications on in vitro antioxidant activity
Fisetin (3,3',4',7-tetrahydroxyflavone) has been investigated for its ability to bind iron in a wide range of pH values of acetate and phosphate buffered solutions. To assess the relevant interactions of iron with fisetin, combined spectroscopic (UV/visible, Raman, MS) and theoretical appr...
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Published in: | Dalton transactions : an international journal of inorganic chemistry 2011-05, Vol.40 (17), p.4560-4571 |
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description | Fisetin (3,3',4',7-tetrahydroxyflavone) has been investigated for its ability to bind iron in a wide range of pH values of acetate and phosphate buffered solutions. To assess the relevant interactions of iron with fisetin, combined spectroscopic (UV/visible, Raman, MS) and theoretical approaches were used. The chelation sites, stoichiometry, stability and the dependence of the complexes structures on pH were defined. The results pointed to the formation of two iron-fisetin complexes with stoichiometries of 1 : 1 and 1 : 2, depending on the pH. Results of vibrational analysis and theoretical calculations implicated the 3-hydroxyl-4-carbonyl group as a chelating site in acidic media while catechol (3'-hydroxyl-4'-hydroxyl) group was identified as the chelating group in neutral and alkaline media. Determined relative, conditional, stability constants with iron-fisetin were in the range from 6 × 10(4) dm(3) mol(-1) to 7 × 10(9) dm(6) mol(-2). Competition experiments demonstrated that fisetin bound iron less strongly than EDTA and citric acid under the investigated experimental conditions. Rate constant values calculated for the fast step of the DPPH reduction for fisetin and the iron-fisetin complex are k(1) = 225.75 dm(3) mol(-1) s(-1) and k(1) = 658.00 dm(3) mol(-1) s(-1). These values fit within the interval of the rate constant values which are typical for antioxidants which have a single polyphenolic nucleus. The equilibrium geometries, optimized at the B3LYP/6-311 + G(d,p) and M06/6-311 + G(d,p) levels of theory, predicted structural modifications between the ligand molecule in the free state and in the complex structure. The theoretical model has been validated by both vibrational and electronic spectroscopies. |
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Implications on in vitro antioxidant activity</title><source>Royal Society of Chemistry</source><creator>Dimitrić Marković, Jasmina M ; Marković, Zoran S ; Brdarić, Tanja P ; Filipović, Nenad D</creator><creatorcontrib>Dimitrić Marković, Jasmina M ; Marković, Zoran S ; Brdarić, Tanja P ; Filipović, Nenad D</creatorcontrib><description>Fisetin (3,3',4',7-tetrahydroxyflavone) has been investigated for its ability to bind iron in a wide range of pH values of acetate and phosphate buffered solutions. To assess the relevant interactions of iron with fisetin, combined spectroscopic (UV/visible, Raman, MS) and theoretical approaches were used. The chelation sites, stoichiometry, stability and the dependence of the complexes structures on pH were defined. The results pointed to the formation of two iron-fisetin complexes with stoichiometries of 1 : 1 and 1 : 2, depending on the pH. Results of vibrational analysis and theoretical calculations implicated the 3-hydroxyl-4-carbonyl group as a chelating site in acidic media while catechol (3'-hydroxyl-4'-hydroxyl) group was identified as the chelating group in neutral and alkaline media. Determined relative, conditional, stability constants with iron-fisetin were in the range from 6 × 10(4) dm(3) mol(-1) to 7 × 10(9) dm(6) mol(-2). Competition experiments demonstrated that fisetin bound iron less strongly than EDTA and citric acid under the investigated experimental conditions. Rate constant values calculated for the fast step of the DPPH reduction for fisetin and the iron-fisetin complex are k(1) = 225.75 dm(3) mol(-1) s(-1) and k(1) = 658.00 dm(3) mol(-1) s(-1). These values fit within the interval of the rate constant values which are typical for antioxidants which have a single polyphenolic nucleus. The equilibrium geometries, optimized at the B3LYP/6-311 + G(d,p) and M06/6-311 + G(d,p) levels of theory, predicted structural modifications between the ligand molecule in the free state and in the complex structure. The theoretical model has been validated by both vibrational and electronic spectroscopies.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c0dt01834a</identifier><identifier>PMID: 21431152</identifier><language>eng</language><publisher>England</publisher><subject>Antioxidants - chemistry ; Biphenyl Compounds - chemistry ; Buffers ; Chelating Agents - chemistry ; Flavonoids - chemistry ; Hydrogen-Ion Concentration ; Iron - chemistry ; Picrates - chemistry ; Quantum Theory ; Solutions - chemistry ; Water - chemistry</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2011-05, Vol.40 (17), p.4560-4571</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c356t-512919ed05b78b3a1e6e77be2eb76c9e07bf0336de7714b833a5d5471084830b3</citedby><cites>FETCH-LOGICAL-c356t-512919ed05b78b3a1e6e77be2eb76c9e07bf0336de7714b833a5d5471084830b3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,786,790,27957,27958</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/21431152$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Dimitrić Marković, Jasmina M</creatorcontrib><creatorcontrib>Marković, Zoran S</creatorcontrib><creatorcontrib>Brdarić, Tanja P</creatorcontrib><creatorcontrib>Filipović, Nenad D</creatorcontrib><title>Comparative spectroscopic and mechanistic study of chelation properties of fisetin with iron in aqueous buffered solutions. Implications on in vitro antioxidant activity</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>Fisetin (3,3',4',7-tetrahydroxyflavone) has been investigated for its ability to bind iron in a wide range of pH values of acetate and phosphate buffered solutions. To assess the relevant interactions of iron with fisetin, combined spectroscopic (UV/visible, Raman, MS) and theoretical approaches were used. The chelation sites, stoichiometry, stability and the dependence of the complexes structures on pH were defined. The results pointed to the formation of two iron-fisetin complexes with stoichiometries of 1 : 1 and 1 : 2, depending on the pH. Results of vibrational analysis and theoretical calculations implicated the 3-hydroxyl-4-carbonyl group as a chelating site in acidic media while catechol (3'-hydroxyl-4'-hydroxyl) group was identified as the chelating group in neutral and alkaline media. Determined relative, conditional, stability constants with iron-fisetin were in the range from 6 × 10(4) dm(3) mol(-1) to 7 × 10(9) dm(6) mol(-2). Competition experiments demonstrated that fisetin bound iron less strongly than EDTA and citric acid under the investigated experimental conditions. Rate constant values calculated for the fast step of the DPPH reduction for fisetin and the iron-fisetin complex are k(1) = 225.75 dm(3) mol(-1) s(-1) and k(1) = 658.00 dm(3) mol(-1) s(-1). These values fit within the interval of the rate constant values which are typical for antioxidants which have a single polyphenolic nucleus. The equilibrium geometries, optimized at the B3LYP/6-311 + G(d,p) and M06/6-311 + G(d,p) levels of theory, predicted structural modifications between the ligand molecule in the free state and in the complex structure. The theoretical model has been validated by both vibrational and electronic spectroscopies.</description><subject>Antioxidants - chemistry</subject><subject>Biphenyl Compounds - chemistry</subject><subject>Buffers</subject><subject>Chelating Agents - chemistry</subject><subject>Flavonoids - chemistry</subject><subject>Hydrogen-Ion Concentration</subject><subject>Iron - chemistry</subject><subject>Picrates - chemistry</subject><subject>Quantum Theory</subject><subject>Solutions - chemistry</subject><subject>Water - chemistry</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2011</creationdate><recordtype>article</recordtype><recordid>eNpFUclOwzAUtBCIlsKFD0C-ISG1eEni5IgqlkqVuMA58vKiGmXDdgr9JP4Sd6Gcnt943nieB6FrSmaU8OJeExMIzXkiT9CYJkJMC8aT0-OZZSN04f0HIYyRlJ2jEaMJpzRlY_Qz75peOhnsGrDvQQfXed31VmPZGtyAXsnW-hB7HwazwV2F9QrqONC1uHddDy5Y8Fu8sh6CbfGXDStsXbyPjfwcoBs8VkNVgQODfVcP22E_w4umr63eSUWBHX1to4H4dMS-rYkVSx292bC5RGeVrD1cHeoEvT89vs1fpsvX58X8YTnVPM3CNKWsoAUYkiqRKy4pZCCEAgZKZLoAIlRFOM9MRGmics5latJEUJInOSeKT9DtXjcuF737UDbWa6hr2W4XKfOMJywlgkTm3Z6p4595B1XZO9tItykpKbfJlP_JRPLNQXZQDZgj9S8K_guT5Y5J</recordid><startdate>20110507</startdate><enddate>20110507</enddate><creator>Dimitrić Marković, Jasmina M</creator><creator>Marković, Zoran S</creator><creator>Brdarić, Tanja P</creator><creator>Filipović, Nenad D</creator><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20110507</creationdate><title>Comparative spectroscopic and mechanistic study of chelation properties of fisetin with iron in aqueous buffered solutions. Implications on in vitro antioxidant activity</title><author>Dimitrić Marković, Jasmina M ; Marković, Zoran S ; Brdarić, Tanja P ; Filipović, Nenad D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c356t-512919ed05b78b3a1e6e77be2eb76c9e07bf0336de7714b833a5d5471084830b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2011</creationdate><topic>Antioxidants - chemistry</topic><topic>Biphenyl Compounds - chemistry</topic><topic>Buffers</topic><topic>Chelating Agents - chemistry</topic><topic>Flavonoids - chemistry</topic><topic>Hydrogen-Ion Concentration</topic><topic>Iron - chemistry</topic><topic>Picrates - chemistry</topic><topic>Quantum Theory</topic><topic>Solutions - chemistry</topic><topic>Water - chemistry</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Dimitrić Marković, Jasmina M</creatorcontrib><creatorcontrib>Marković, Zoran S</creatorcontrib><creatorcontrib>Brdarić, Tanja P</creatorcontrib><creatorcontrib>Filipović, Nenad D</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Dimitrić Marković, Jasmina M</au><au>Marković, Zoran S</au><au>Brdarić, Tanja P</au><au>Filipović, Nenad D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Comparative spectroscopic and mechanistic study of chelation properties of fisetin with iron in aqueous buffered solutions. Implications on in vitro antioxidant activity</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2011-05-07</date><risdate>2011</risdate><volume>40</volume><issue>17</issue><spage>4560</spage><epage>4571</epage><pages>4560-4571</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><notes>ObjectType-Article-1</notes><notes>SourceType-Scholarly Journals-1</notes><notes>ObjectType-Feature-2</notes><notes>content type line 23</notes><abstract>Fisetin (3,3',4',7-tetrahydroxyflavone) has been investigated for its ability to bind iron in a wide range of pH values of acetate and phosphate buffered solutions. To assess the relevant interactions of iron with fisetin, combined spectroscopic (UV/visible, Raman, MS) and theoretical approaches were used. The chelation sites, stoichiometry, stability and the dependence of the complexes structures on pH were defined. The results pointed to the formation of two iron-fisetin complexes with stoichiometries of 1 : 1 and 1 : 2, depending on the pH. Results of vibrational analysis and theoretical calculations implicated the 3-hydroxyl-4-carbonyl group as a chelating site in acidic media while catechol (3'-hydroxyl-4'-hydroxyl) group was identified as the chelating group in neutral and alkaline media. Determined relative, conditional, stability constants with iron-fisetin were in the range from 6 × 10(4) dm(3) mol(-1) to 7 × 10(9) dm(6) mol(-2). Competition experiments demonstrated that fisetin bound iron less strongly than EDTA and citric acid under the investigated experimental conditions. Rate constant values calculated for the fast step of the DPPH reduction for fisetin and the iron-fisetin complex are k(1) = 225.75 dm(3) mol(-1) s(-1) and k(1) = 658.00 dm(3) mol(-1) s(-1). These values fit within the interval of the rate constant values which are typical for antioxidants which have a single polyphenolic nucleus. The equilibrium geometries, optimized at the B3LYP/6-311 + G(d,p) and M06/6-311 + G(d,p) levels of theory, predicted structural modifications between the ligand molecule in the free state and in the complex structure. The theoretical model has been validated by both vibrational and electronic spectroscopies.</abstract><cop>England</cop><pmid>21431152</pmid><doi>10.1039/c0dt01834a</doi><tpages>12</tpages></addata></record> |
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subjects | Antioxidants - chemistry Biphenyl Compounds - chemistry Buffers Chelating Agents - chemistry Flavonoids - chemistry Hydrogen-Ion Concentration Iron - chemistry Picrates - chemistry Quantum Theory Solutions - chemistry Water - chemistry |
title | Comparative spectroscopic and mechanistic study of chelation properties of fisetin with iron in aqueous buffered solutions. Implications on in vitro antioxidant activity |
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